JPH0439396A - Emulsion type rust preventing wax - Google Patents

Abstract

PURPOSE:To obtain the subject wax, containing a specific wax, a liquid polymer, an emulsion type synthetic resin, a half ester of an alkyl-substituted succinic acid, an organic amine and water and capable of imparting high rust preventing performance with a relatively thin dried film. CONSTITUTION:The objective wax containing (A) 100pts.wt. wax, composed of an oxide of paraffin wax, an oxide of polyethylene wax, etc., and having carboxyl groups, (B) 15-50pts.wt. liquid polymer such as liquid polybutadiene or liquid polyisoprene, (C) 5-50pts.wt. emulsion type synthetic resin (solid) such as an alkyd resin or an acrylic resin, (D) 5-50pts.wt. half ester of an alkyl- substituted succinic acid, (E) 15-45pts.wt. organic amine such as N,N- dimethylethanolamine or triethanolamine and (F) water. The aforementioned wax is especially useful for coating the interior of engine rooms in car bodies.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to an emulsion-type rust-preventing wax used mainly for rust-preventing the body of an automobile, and particularly to an emulsion-type rust-preventing wax that is applied to the engine room of a car body to form a rust-preventive coating film. This invention relates to an emulsion-type rust-preventing wax useful for forming.

[Conventional technology] Conventionally, rust prevention in the engine room of automobiles has been done using rust preventive agents such as petrolatum oxide metal salts, ester waxes, and petroleum sulfonic acid metal salts dispersed in organic solvents such as mineral oil or mineral spirits, and paraffin. Corrosion inhibitors have been used in which waxes, microcrystalline waxes, and oxidized paraffin metal salts are dispersed in mineral spirits. In recent years, in order to avoid environmental and pollution problems caused by organic solvents, attempts have been made to switch from the above-mentioned organic solvent type to aqueous type rust inhibitors, and their formulation compositions have been proposed. Examples of emulsion type products include JP-A-63-17
No. 993 discloses a mixture of a wax with a carboxyl group and a wax without a carboxyl group, mineral oil,
There is a disclosure of a water-in-oil emulsion rust-preventing wax consisting of an organic amine and water. Also, JP-A-63-17509
No. 8 discloses an emulsion type rust preventive agent consisting of a wax having a carboxyl group, a microcrystalline wax, an organic amine, a water-soluble resin, a non-ferrous metal rust preventive agent, and water.

With conventional solvent-based rust preventive agents, it is known that adding ester wax is effective in improving the rust preventive performance of thin coating films.

However, this ester wax has water repellency and is difficult to add to emulsion-type antirust wax. In addition, it has been proposed that salts of alkyl-substituted succinic acid half esters are effective as water-soluble rust preventives (JP-A-61-1999).
No. 56287), as an emulsion type rust preventive agent, it cannot be present in the coating film as it is, and it is difficult to improve the rust preventive properties of the dry film.

[Problems to be Solved by the Invention] The above-mentioned emulsion-type rust-preventing wax has wax as its main rust-preventing component, and other additives are blended in order to form an emulsion and form a uniform rust-preventing coating film. . This emulsion-type antirust wax needs to have a dry coating film of at least 50 μm or more in order to obtain high antirust properties. However, since this oxidized wax, which is the main component, is opaque, if the film is thick enough to exhibit rust-preventive properties, it becomes opaque and the appearance of the coating film deteriorates, which is not preferable. For this reason, there is a need for an emulsion-type rust-preventing wax that has sufficient rust-preventing performance and has a thin film thickness that does not cause defects in the appearance of the dried coating film.

The present invention was made in view of the above circumstances, and an object of the present invention is to provide an emulsion-type rust-preventing wax that can provide high rust-preventing performance with a relatively thin dry coating film.

[Means for Solving the Problems] The emulsion-type antirust wax of the present invention contains (B) based on 100 parts by weight of wax having a carboxyl group (A).
15 to 50 parts by weight of liquid polymer, 5 to 50 parts by weight of (C) emulsion type synthetic resin (solid content), 5 to 50 parts by weight of (D>alkyl purchased succinic acid hafester),
It is characterized by containing 15 to 45 parts by weight of (E) an organic amine and (F) water.

The wax having a carboxyl group (A>) used in the present invention is neutralized with carboxyl (E) and emulsified. Therefore, it is preferable that the wax has an acid value in the range of 10 to 50ffffKOH/7. If it is less than 107F!ffKOH/9, the emulsion will become unstable and the acid value will be 501ngKOH/
If it exceeds g, the rust prevention properties will deteriorate, which is not preferable. This wax component is the main component that coats the surface of the steel plate to form a rust preventive film.

As the wax having a carboxyl group, for example, paraffin wax oxide, microcrystalline wax oxide, petrolatum oxide, polyethylene wax oxide, etc. can be used.

The liquid polymer (B) is a component that imparts plasticity to the rust-preventing coating and maintains rust-preventing properties as a stable film even when the dry film thickness is reduced. Examples include liquid polybutadiene, liquid polyisoprene, and liquid polybutene. etc. can be used.

The amount of component (B) added is 15 to 50 parts by weight per 100 parts by weight of wax (Δ). If the amount added is less than 15 parts by weight, no effect will be observed, and if it exceeds 50 parts by weight, the proportion of the rust-preventing component will decrease, resulting in a decrease in rust-preventing properties, and cracks will occur in the rust-preventing film, so it is preferable. do not have.

The emulsion type synthetic resin (C) is a component that stably disperses the active ingredient in the emulsion, and for example, emulsified products such as alkyd resin, acrylic resin, and acrylic-styrene copolymer can be used.

The amount of component (C) added is 5 to 50 parts by weight per 100 parts by weight of wax (A). If the amount added is less than 5 parts by weight, it will be difficult to maintain the viscosity of the emulsion stably, increase the applicability and maintain storage stability, and if it exceeds 50,000 m1 part, the proportion of the rust preventive component will decrease and the rust preventive properties will be reduced. This is undesirable because it lowers the coating properties and deteriorates the coating properties.

The alkyl-substituted succinic acid half ester (D) is formed by adding an alkyl group to the double bond of maleic acid, and the alkyl group has 8 to 24 carbon atoms.
(R1, R2, R3) having one or two substituents can be used and is represented by the following formula.

HOOCCH2CHRt C00R4 HOOCCH2CHR3GOOR4 Alcohol that forms half ester with succinic acid (R4
) can be an alkyl alcohol having 1 to 18 carbon atoms.

The amount of component (D) added is 5 to 50 parts by weight per 100 parts by weight of wax (A). If the amount added is less than 5 parts by weight, the rust prevention properties will deteriorate, and if it exceeds 50 parts by weight, the emulsion will become unstable, which is not preferable. In this succinic acid, one of the carboxyl groups is esterified and the other exists as a carboxyl group. This carboxyl group is neutralized with the organic amine (E) to form a salt.

Examples of the organic amine (E) include N,N-dimethylethanolamine, N,N-diethylethanolamine, and N(
β-aminoethanol) ethanolamine, N-methylethanolamine, N-methylgetanolamine, morpholine, monoethanolamine, jetanolamine,
Triethanolamine etc. can be used. This organic amine neutralizes carboxyl groups to form amine salts and stabilize the emulsion. It hardly remains in the dry coating film and scatters with water.

The amount of component (E) added is 15 to 50 parts by weight per 100 parts by weight of wax (A). If the amount added is less than 15 parts by weight, the emulsion will become unstable, and if it exceeds 50 parts by weight, the water resistance of the coating film will decrease, which is not preferable.

Each of the above components is dispersed as an emulsion in water (F), but adjusting the concentration so that the solid content is 15 to 30% is the best way to apply it to form a thin dry coating uniformly. preferred.

The above emulsion type anti-rust waxes are (A>, (B),
In addition to the components (C), (D>, (E), and (F)), rust preventive additives, surfactants, viscosity modifiers, wettability improvers, leveling agents, preservatives, etc. may be added as necessary. It can be added as appropriate.

There are no particular restrictions on the method for preparing this emulsion-type antirust wax, but for example, first, a mixture of (A>, (B), and (D)) is heated to uniformly dissolve it, and then (E) is added and stirred. to make a homogeneous mixture. This mixture was heated (F
) in water to form an emulsion. Furthermore, (C) is added to this emulsion while stirring to form the desired emulsion.

This emulsion-type rust-preventive wax can be applied by spraying, brushing, etc. to form a rust-preventive coating.

Therefore, as in the present invention, a stable emulsion can be formed by blending a wax with a carboxyl group, a liquid polymer, an emulsion type synthetic resin, and an organic amine in a specific composition, and the application of this emulsion allows for dry coating with a thin film thickness. Even a film can provide sufficient rust prevention properties.

[Function] This emulsion-type antirust wax can form a stable emulsion by having the above composition. This emulsion has excellent storage stability, no contamination of the coating film, and excellent coating properties.The dry coating film formed has a thickness of 50 μm.
It exhibits high rust prevention properties even with a small film thickness of less than m. That is, it is presumed that an excellent rust-preventing film is formed by appropriately blending each component. In particular, by adding an alkyl-substituted succinic acid half ester, it is possible to form a film exhibiting excellent rust prevention properties even with a thin film thickness.

[Example] Hereinafter, this will be explained in detail with reference to Examples.

(Example 1) This emulsion-type antirust wax was prepared as follows.

Acid value 38# as wax with carboxyl group (△)
IgKOH/g of “Nikrocrystalline wax 1”
2 parts by weight, 24 parts by weight of Poly 1F with a molecular weight of 300 as the liquid polymer (B), and an acid value of 70 m as the alkyl-substituted succinic acid half ester (D)! jKO1-1/g, Molecule 1704, (manufactured by Parker Kosan AT) 3 parts by weight were dissolved in a beaker by heating (90 to 95° C.) with stirring to form a homogeneous mixture. To this mixture, 3 parts by weight of N,N=nidimethylethanolamine is added as the organic amine (E), and the mixture is stirred for at least 5 minutes while maintaining the liquid temperature at 90 to 95°C. Furthermore, the liquid temperature of this organic amine addition mixture was adjusted to 90 to 9
While maintaining the temperature at 5° C. and stirring, 73 parts by weight of water (F) was added to form an emulsion. This emulsion was further cooled while stirring, and when the liquid temperature reached 40°C, 5% of the emulsion type synthetic resin (C) acrylic-styrene copolymer (trade name VONOCOAT EC710 manufactured by Dainippon Ink ■) (solid content 40%) was added. An emulsion-type antirust wax was prepared by adding part by weight.

(Evaluation) After degreasing with trichlorethylene vapor in advance, an air gun (W-71 made by Iwata Yaiki ■) was placed on a JIS G 3141 dull steel plate (SPCC-3DI plate 150X70X0.8#) whose surface was adjusted with warm methanol. After applying an emulsion-type rust-preventing wax to a dry film thickness of 20 μm, the sample was left at room temperature for one week, and the following performance tests were conducted.

(Performance evaluation items and methods for coating films) (1) Salt spray test: A salt spray test based on γM according to JIS K2246 was conducted to examine the degree of rust occurrence.

(2) Wet test: A wet test based on JIS K2246 was conducted to examine the degree of rust occurrence.

(3) Cycle test: The above salt spray test was carried out for 17 hours, 5
The degree of rust generation was examined after 10 cycles of 3 hours of drying at 0°C, 2 hours of immersion in salt water at 20°C, and 2 hours of standing indoors.

(4) Storage stability test: 300rrd sealed! A sample was placed in a plastic container and allowed to stand at room temperature for one week, after which the degree of viscosity thickening was visually examined.

(5) Paint film staining test: Painted board (150x70x0.8
Inner diameter 30M, height 15 on top of # automobile top coated plate)
Place a polyethylene cylinder of size M and firmly adhere it to the painted plate using a rubber band, etc., and after dropping 2 d of sample into the opening,
After being left in a dryer at ℃ for 4 hours, the sample was removed and the appearance was visually inspected.

The results are shown in Table 1. In addition, the rust occurrence degree in the table is the rust occurrence area A: 0%, B: 1-10%, C: 11-25%.
, D: 26-50%, [: 51-100%. Storage stability is expressed as Q: No change, △: Slightly thickened, X: Thickened and gelled, and paint film staining property is expressed as ○: No change, △: Slightly swelling, X: Swelling □ Must. , expressed as

(Example 2) As shown in Table 1, the wax (A) of Example 1 and the acid value 1
It was formed by using two types of 4m3KOH/'J of botu ethylene wax together and adding an alkaline earth metal salt of G oil sulfonic acid as a rust preventive additive.

(Example 3) This is an alkyl-substituted alkyl succinic acid half ester (
D>'s Mlllli70m'j K OH/7 molecules foot 561 Parker Kosan (l Same as Example 1 except that a wooden one was used.

(Example 4) This is the same as Example 1 except that the organic amine (H) was replaced with morpholine.

(Comparative Example 1) This rust preventive agent consists of petrolatum oxide metal salt (petrolatum barium oxide salt), ester wax (methyl ester wax), petroleum sulfonate metal salt (petroleum sulfonate barium salt), mineral oil, mineral spirit (boiling point 150 ~
200°C) and the composition ratios are shown in Table 2.

(Comparative Example 2) This rust preventive agent consists of paraffin wax (paraffin wax with a melting point of 50°C), microcrystalline wax (microcrystalline wax with a melting point of 70°C), paraffin oxide metal salt (paraffin oxide calcium salt), mineral spirit (boiling point 150°C), ~200'C), and the composition ratios are shown in Table 2.

(Comparative Example 3) As shown in Table 1, this rust preventive agent is the same as in Example 1 but does not contain the alkyl-substituted succinic acid half ester (D>).

These rust preventives were evaluated in the same manner as in Example 1, and the results are shown in Table 1.2.

In the example, compared with the solvent-based comparative example 1.2 at the same dry film thickness, the salt spray test and cycle test were significantly improved. However, in the example, the dry film thickness was 20 μm.
In contrast, rust occurred in more than half of the area of the test piece in the comparative example, whereas rust occurred in less than 10% even with m. Furthermore, when the component (D>) of Comparative Example 3 was not included, the occurrence of rust was significant in both the salt spray test, wet abrasion test, and cycle test.

Although the storage stability and coating film staining properties in the examples are somewhat lower than those of the solvent type, they have sufficient performance for practical use.

[Effects] As described above, the emulsion-type antirust wax of the present invention exhibits high antirust properties even with a thin film thickness. Therefore, even if it is applied to the engine room of a car, the film thickness can be reduced, so the transparency is good and the aesthetics of the engine room can be improved.

Patent Applicant l~Yota Jidosha Co., Ltd. Patent Applicant
Parker Kosan Co., Ltd.

Claims (1)

[Claims] (1) (A) 100 parts by weight of wax having a carboxyl group, (B) 15 to 50 parts by weight of liquid polymer, (C) 5 to 50 parts by weight of emulsion type synthetic resin (solid content), ( D) Alkyl substituted succinic acid half ester is 5 to 50
(E) 15 to 45 parts by weight of an organic amine; and (F) water.